Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS4814000 A
Publication typeGrant
Application numberUS 06/902,131
Publication dateMar 21, 1989
Filing dateSep 2, 1986
Priority dateAug 13, 1982
Fee statusLapsed
Also published asDE3368176D1, EP0102003A1, EP0102003B1
Publication number06902131, 902131, US 4814000 A, US 4814000A, US-A-4814000, US4814000 A, US4814000A
InventorsBaldo Ciocca, Attilio Formigoni, Gino Epis
Original AssigneeS.I.P.C.A.M. S.p.A - Societa Italiana Prodotti Chimici e per l'Agricoltura Milano
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Stabilized herbicide composition based on meta-biscarbamates
US 4814000 A
Abstract
A chemically stabilized herbicide composition containing the compound with the formula: ##STR1## together with tristyryl-phenol-phosphates-polyethoxylated and/or polypropoxylated as well as with other possible coadjuvant and inert substances.
Images(5)
Previous page
Next page
Claims(7)
We claim:
1. An herbicide composition with chemical stability of the active ingredient formulated as an organic solvent-base emulsifiable liquid comprising an effective amount of the compound of formula: ##STR4## together with a chemical stabilizer selected from the group consisting of tristyryl-phenol-phosphate polyethoxylated, tristyryl-phenol-phosphate polypropoxylated and mixtures thereof along with other coadjuvants and inerts.
2. The composition as claimed in claim 1, wherein the tristyryl-phenol-phosphate polyethoxylated is formed from 6-25 moles of ethylene oxide.
3. The composition as claimed in claim 1, wherein the tristyryl-phenol-phosphate polypropoxylated is formed from 6-25 moles of propylene oxide.
4. The composition as claimed in claim 1 wherein the tristyryl-phenol-phosphate polyethoxylated and polypropoxylated have a ratio of 10:1 to 1:1 between ethylene oxide and propylene oxide.
5. The composition as claimed in claim 1 wherein the compound of formula A is contained in the quantity of 10 to 25 percent.
6. The composition as claimed in claim 1 wherein the ratio in weight between the stabilizer and the compound of formula A is comprised between 1:10 and 1.5:1.
7. Process for weed control comprising applying the composition of claim 1 at the rate from 0.23 to 1.5 kg per hectare to the weeds.
Description

This application is a continuation-in-part of application Ser. No. 750,254 filed July 1, 1985 which in turn is a continuation-in-part of application Ser. No. 521,836 filed Aug. 10, 1983, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a chemically stabilised herbicide composition based on meta-biscarbamates.

It is known that herbicide composition containing a compound of formula: ##STR2## or 3-methoxycarbonyl-aminophenyl-N-(3-methylphenyl)carbamate possess excellent herbicide action on sugar beet and other crops, if formulated with suitable adjuvants and inerts.

However, it is also known that the aforesaid compounds possess limited chemical stability with time if prepared in common emulsifiable liquid herbicide compositions based on organic solvents, and which contain adjuvants having no stabilising effect.

U.S. Pat. No. 3,898,075 describe the possibility of stabilising the compoundof formula (A) in emulsifiable liquid herbicide compositions based on organic solvents, by adding a chemical stabilising compound chosen from dicarboxylic aliphatic acids, hydrocarboxylic aliphatic acids, nitro-substituted monocarboxylic aromatic acids, dicarboxylic aromatic acids, sulphonated aliphatic acids, and sulphonated aromatic acids. In addition to claiming these stabilisers, the aforesaid U.S. Patent described the already known addition of common surfactants and inerts commonly used by the expert in this field for preparing emulsifiable liquid composition suitable for use as plant protection products.

Specifically, stated suitable inerts are solvents based on aromatic hydrocarbons, cyclohexanone, isophorone, methylhexahydronaphtalene, dibutylphthalate, tetrahydrophthalene, dimethylsulphoxide and dimethylformamide, and stated suitable surfactants not acting as chemical stabilizers are polyethoxylated amines, alcohols, acids and alkylphenols, and salts of alkylbenzene and naphthalenesulphonic acids.

SUMMARY OF THE INVENTION

With the present invention, it has been unexpectedly found that the compound of formula ##STR3## formulated as emulsifiable liquid, can be chemically stabilized with the addition to the formulation of tri-styryl-phenol-phosphates polyethoxylated and/or polypropoxylated, containing 6-25 moles of ethylene oxide and/or propylene oxide (in ratio of from 10:1 to 1:1 if both oxides are present).

Examples of the aforesaid stabilizers, which are usable in organic solvent-based emulsifiable liquid formulations are:

1. tristyril-phenol-phosphates-polyethoxylated with 17 moles of ethylene oxide (available commercially for example under the names SOPROPHOR 3D33 or SOPRAL 3D 33 or Messrs. SOPROSOIE CO. of Rochetaillee, France, or under the name SOITEM 8 FL of Messrs. SOITEM CO. Milan, Italy);

2. Tristyryl-phenol-phosphate-polyethoxylated with 6 moles of ethylene oxide (available commercially as SOITEM 3 FL of Messrs. SOITEM CO., Milan, Italy).

3. Tristyryl-phenol-phosphate-polypropoxylated with 25 moles of propylene oxide (available commercially as SOITEM 25 P of SOITEM CO. Milan, Italy).

4. A mixture of tristyril phenol phosphates polyethoxylated and polypropoxylated, with 20 moles of ethylene oxyde and 5 moles of propylene oxide (available commercially as SOITEM 8 EP of Messrs. SOITEM CO. Milan, Italy).

With respect to the previous known art, the interest of the present invention is even greater when considering that the tristyryl phenol phosphates polyethoxylated and/or polypropoxylated--cited hereabove--able to exhibit a chemical stabilising effect, also possess the property of acting as surfactants, ie as emulsifying agents, in herbicide formulations of emulsifiable liquids based on compound of formula (A), with obvious saving in adjuvants and greater composition economy.

The discovery was completely unattended because the surfactants used by the prior art for emulsifiable liquid compositions based on compound of formula (A), surfactants that can be eventually used also for increasing the biological activity of the compound of formula (A), are chemically different from those claimed in the present invention and--above all--do not show chemical stabilising activity on emulsifiable liquid compositions of compounds of formula (A) as demonstrated in the Table No. 1.

Additionally, it is known that some inorganic and/or organic acids are not active as stabilizers of emulsifiable liquid compositions of the compound of formula (A) and particularly the phosphoric acid, or acetic acid, do not act as stabilizers, as documented in Table No. 1.

Furthermore phenol derivatives as tristyryl-phenol are not active as stabilizers of compositions of formula (A), as reported also in Table No. 1. To the contrary the tri-styryl-phenol phosphates polyethoxylated and/or polypropylated of the invention are particularly active as stabilizers (see Table No. 1).

                                  TABLE NO. 1__________________________________________________________________________Stabilizing activity of some compounds on the emulsifiable liquidcomposi-tion, having following ingredients:__________________________________________________________________________(1) Active Substance: Compound of formula (A) of 97% purity 172 g(2) Surfactants: as reported, in weight(3) Stabilizers: as reported, in weight(4) Solvent: Isophorone up to 1000 g__________________________________________________________________________                     % Decomposition of Compound                     of formula (A) afterSurfactants    Possible Stabilizers                 T                     1 month 3 months__________________________________________________________________________20% of a mixture    None         20 C.                     3       10of Polethoxy-         54 C.                     30      60lated alkylphenol,    +1% of phosphoric acid                 20 C.                     5       9polyethoxylated       54 C.                     30      55fatty acid, and    +1% of acetic acid                 20 C.                     6       12calcium dodecyl       54 C.                     33      65benzensulfonate    +3,5% of tristyryl-phenol                 20 C.                     8       14                 54 C.                     35      733.5% tristyrylphenolphosphate                 20 C.                     <0.1    <0.2polyethoxylated with 17moles of ethylene oxide(according to the invention)+1.5% calcium dodecylbenzene                 54 C.                     <0.5    <1sulfonate9.5% tristyrylphenolphosphate                 20  C.                     <0.1    <0.2polyethoxylated with 20moles of ethylene oxideand polypropoxylated with5 moles of propylene oxide                 54 C.                     <0.5    <1(according to the invention)15% tristyrylphenolphosphate                 20 C.                     <0.1    <2polypropoxylated with 25moles of propylene oxide                 54 C.                     <0.5    <1(according to the invention)__________________________________________________________________________

It is totally unattended that tri-styryl-phenol-phosphates polyethoxylated, show high stabilizing activity on the compound of formula (A), whereas both trystyrilphenol and phosphoric acid do not show any stabilizing effect.

Moreover, all the stabilisers according to the invention exhibit their activity in relatively small doses, for the most part economical. In this respect, said stabilisers can be added to the compound of formula (A) in a ratio that can be varied between 1:10 and 2.5:1, according to the type of formulation and the concentration of the compound of formula (A). In addition to the stabilisers, with possible surfactant effect according to the invention, other surfactants, suspending agents or emulsifying agents can be added to formulations of the compound of formula (A), as necessary for optimising the hydrophilic/lipophilic balance of the composition in accordance with the methods well known to the skilled man of the art (for example calcium alkylarylsulphonate, polyethoxylated fatty acids, polyethoxylated alkylarylphenols and others, as described in the publication McCutcheon's--Detergent & Emulsifiers--1982 Annual--International Edition, Glen Rock (N.J.) U.S.A.).

Other active pesticides or adjuvant substances can also be added to the formulations according to the invention, in particular other herbicides, such as chloridazon, metamitron, ethofumesate, lenacil, cycloate, diallate, triallate, butachlor, metolachlor, trimexachlor and others. For organic solvent-based liquid formulations which are emulsifiable in water, the following composition can be used by way of example:

10-25% (preferably 15-20%) of active substance of formula (A);

1-25% (preferably 2-10%) of stabiliser, which may also possess emulsifying action, possibly together with a further surfactant not possessing stabilising activity.

Remainder to 100% of solvents, together with other emulsifiers, if necessary. The solvents used can be isophorone, cyclohexanone, aromatic hydrocarbons, naphta solvent, dimethylsulphoxide, dimethylformamide, N-methylpyrrolidone and others.

The composition according to the invention is particularly suitable for use in the selective weed control of agricultural or horticultural crops (such as sugar beet, fodder beet, red beet, spinach, strawberries, etc.) mainly in treatment after weeds emergence, by spraying dilute aqueous emulsions or suspension containing from 0.23 to 1.5 Kg/Ha of active substance.

The following examples are useful for better illustrating the invention, but do not limit its possible applications.

EXAMPLE NO. 1

The following substance are fed into a vessel fitted with a liquid stirrer, and are kept constantly mixed:

______________________________________            Formula I                     Formula II______________________________________Compound of formula (A) with 97%              17.2 Kg.   17.2 Kg.puritySOITEM 8 FL (1)    7.0 Kg.     1.7 Kg.Calcium dodecylbenzenesulphonate              3.0 Kg.     1.0 Kg.Naphta solvent     3.0 Kg.    10.0 Kg.Isophorone         69.8 Kg.   70.1 Kg.TOTAL              100.0 Kg.  100.0 Kg.______________________________________

______________________________________            Formula III                     Formula IV______________________________________Compound of formula (A) with 97%              17.2 Kg.   17.2 Kg.puritySOPROPHOR 3D33 (2) 3.5 Kg.    20.0 Kg.SOITEM 101 (I)     0.5 Kg.     1.0 Kg.SOITEM 990 (1)     2.0 Kg.     3.0 Kg.Naphta solvent     3.0 Kg.    --Isophorone         73.8 Kg.   58.8 Kg.TOTAL              100.0 Kg.  100.0 Kg.______________________________________

______________________________________            Formula V                     Formula VI______________________________________Compound of formula (A) with 97%              11.8       25.5puritySOITEM 8 EP (1)    17.7       --SOITEM 3 FL (I)    --         7.5SOITEM 101 (1)      0.5       2.0SOITEM 990 (1)      3.5       3.0Naphta solvent      3.0       3.0Isophorone         63.5       59.0TOTAL              100.0      100.0______________________________________

Various stabilized emulsifiable liquid formulations are thereby obtained, to be used as herbicides.

(1) Messrs. SOITEM Milan (Italy)

(2) Messrs. SOPROSOIE Rochetaillee (France)

EXAMPLE NO. 2

The chemical stability of the active substance is observed at various temperature levels (20 C., and 54 C.) for various lengths of time (1 month and 3 months) for organic solvent-based emulsifiable liquid formulations, according to the invention, as indicated in Example No. 1, compared with an emulsifiable liquid formulation without stabilisers and having the following composition:

______________________________________Compound of formula (A) with 97% purity                        17.2 Kg.SOITEM 101 (mixture of 80% octylphenol polyethoxy-                        1.0 Kg.lated with 20 moles E.O. with 20% calcium dodecyl-benzenesulfonate).sup.(1)SOITEM 990 (mixture of 25% octylphenol polyethoxy-                        7.0 Kg.lated with 20 moles E.O. with 75% calcium dodecyl-benzenesulfonate).sup.(1)Isophorone                   74.8 Kg.TOTAL                       100.0 Kg.______________________________________ .sup.(1) Produced by SOITEM, Milan (Italy)

After the aging test of 3 months the formulation samples were used in a field with sugar beets of variety Monogem as post-emergence herbicides at the dosage of 2 and 6 l/ha, there being present a mixed population of weeds represented in almost equal proportion by Chenopodium album, Stellaria media, Capsella bursa-pastoris, Solanum nigrum, in a young stage of growth.

Three weeks after the herbicidal treatments the percent reduction of treated weeds was compared to the percent reduction of untreated weeds. No damage to sugar beets with both rates of herbicides was observed. Such results were also reported in the Table No. 1.

From the results shown in Table No. 1, it can be seen that the addition of the chemical stabilisers, according to the invention, prevents the decomposition of the active substance and loss of good herbicidal activity of the formulations, even if the emulsifiable liquid formulation is kept at elevated temperature for a long period.

                                  TABLE NO. 1__________________________________________________________________________Stability of the active substance of formula (A) (3-methoxycarbonyl-amino-phenyl-N-(3-methylphenyl) carbamate) in emulsifiable liquidcompositions,without and with chemical stabilisers according to the invention, after 1monthand 3 months of aging at 20 C. or 54 C. and theiractivity as post-emergenceherbicides after 3 months of aging.                        % Activity on              % Decomp. active                        weeds after                                % Damages              substance after                        3 months at                                on SugarCOMPOSITIONS   T              1 month                   3 months                        6 l/ha                            2 l/ha                                beets__________________________________________________________________________Composition with stabiliser          20 C.              <0.1 <0.2 100 90  0Formula I (Example No. 1)          54 C.              <0.3 <1   99  82  0Composition with stabiliser          20 C.              <0.1 <0.2 99  88  0Formula II (Example No. 1)          54 C.              <0.5 <1   97  80  0Composition with stabiliser          20 C.              <0.1 <0.2 99  89  0Formula III (Example No. 1)          54 C.              <0.5 <2   98  82  0Composition with stabiliser          20 C.              <0.1 <0.2 100 92  0Formula IV (Example No. 1)          54 C.              <0.3 <1   98  86  0Composition with stabiliser          20 C.              <0.1 <0.2 95  82  0Formula V (Example No. 1)          54 C.              <0.3 <1   92  78  0Composition with stabiliser          20 C.              <0.1 <0.2 100 96  0Formula VI (Example No. 1)          54 C.              <0.5 <2   100 95  0Composition without stabiliser          20 C.               3   <10  60  20  0Formula of (Example No. 2)          54 C.               30  <60  25   5  0__________________________________________________________________________ Formula I with stabiliser is a preferred composition.

The results are shows in Table No. 2, from which it can be seen that the addition of the stabilisers, according to the invention, prevents the decomposition of the active substance, even if the emulsifiable liquid formulation is kept at elevated temperature for a long period.

              TABLE NO. 2______________________________________Stability of the active substance of formula (A) (3-methoxycarbonyl-aminophenyl-N--(3-methylphenyl) carbamate) in emulsifiableliquid compositions, with and without stabilisers accordingto the invention.               % Decomposition               active substance afterCOMPOSITIONS     T                     1 month  3 months______________________________________Composition with stabiliser            20 C.                     <0.1     <0.2Formula I (Example No. 1)            54 C.                     <0.3     <1Composition with stabiliser            20 C.                     <0.1     <0.2Formula II (Example No. 1)            54 C.                     <0.5     <1Composition with stabiliser            20 C.                     <0.1     <0.2Formula III (Example No. 1)            54 C.                     <0.5     <2Composition with stabiliser            20 C.                     <0.1     <0.2Formula IV (Example No. 1)            54 C.                     <0.3     <1Composition with stabiliser            20 C.                     <0.1     <0.2Formula V (Example No. 1)            54 C.                     <0.3     <1Composition with stabiliser            20 C.                     <0.1     <0.2Formula VI (Example No. 1)            54 C.                     <0.5     <2Composition without stabiliser            20 C.                      3       <10Formula of (Example No. 2)            54 C.                      30      <60______________________________________
Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3404975 *Nov 15, 1965Oct 8, 1968Fmc Corpm-(carbamoyloxy)-carbanilates as herbicides
US3898075 *Jul 3, 1972Aug 5, 1975Czyzewski AlfredStabilized liquid compositions
US4202684 *Aug 24, 1978May 13, 1980Schering AktiengesellschaftCarbanilic acid esters, process for making the same and herbicidal compositions containing same
US4252557 *Jun 11, 1979Feb 24, 1981Schering AktiengesellschaftM-diurethanes
US4257804 *Apr 10, 1979Mar 24, 1981Schering AktiengesellschaftCarbamic acid ester, process for making the same and composition containing same
US4313847 *May 25, 1979Feb 2, 1982Ici Americas Inc.Surfactant compositions
US4315769 *Nov 21, 1979Feb 16, 1982Schering AgHerbicidaldiurethanes and their use
US4441915 *Jul 15, 1981Apr 10, 1984Schering AktiengesellschaftDiurethanes and herbicidal compositions containing the same
US4461641 *Feb 25, 1982Jul 24, 1984Ciba-Geigy CorporationHerbicidal mixtures
GB1193998A * Title not available
JPS5758601A * Title not available
Non-Patent Citations
Reference
1Bachelot et al., "Aqueous Insecticide, etc.," (1981) CA 95:163933g (1981).
2 *Bachelot et al., Aqueous Insecticide, etc., (1981) CA 95:163933g (1981).
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5082591 *May 30, 1989Jan 21, 1992Rhone-Poulenc ChimieSurface active agent based on polyoxyalkylenated (1-phenyl ethyl) phenols, the process for preparation thereof and the use thereof for producing emulsifiable concentrated solutions of active materials
US5770760 *Apr 2, 1996Jun 23, 1998Rhodia Inc.Polymers useful as pH responsive thickeners and monomers therefor
US5874495 *Jun 7, 1995Feb 23, 1999Rhodia Inc.Polymers useful as PH responsive thickeners and monomers therefor
US6455471 *Feb 8, 1999Sep 24, 2002Syngenta Crop Protection, Inc.Pesticidal compositions
Classifications
U.S. Classification504/301, 504/363
International ClassificationA01N25/22, A01N47/22
Cooperative ClassificationA01N47/22, A01N25/22
European ClassificationA01N47/22, A01N25/22
Legal Events
DateCodeEventDescription
Nov 21, 1986ASAssignment
Owner name: S.I.P.C.A.M. S.P.A. - SOCIETA ITALIANA PRODOTTI CH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CIOCCA, BALDO;FORMIGONI, ATTILIO;EPIS, GINO;REEL/FRAME:004632/0961
Effective date: 19860926
Owner name: S.I.P.C.A.M. S.P.A. - SOCIETA ITALIANA PRODOTTI CH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CIOCCA, BALDO;FORMIGONI, ATTILIO;EPIS, GINO;REEL/FRAME:004632/0961
Effective date: 19860926
Oct 21, 1992REMIMaintenance fee reminder mailed
Mar 21, 1993LAPSLapse for failure to pay maintenance fees
Jun 8, 1993FPExpired due to failure to pay maintenance fee
Effective date: 19930321